Triazinyl anthraquinones

ABSTRACT

NEW FIBRE REACTIVE AZO, ANTHRAQUINONE, FORMAZANE AND PHTHALOCYANINE DYESTUFFS ARE DESCRIBED WHICH POSSESS AS FIBRE REACTIVE MOIETY A CYANAMIDE-TRIAZINYL GROUPING OF THE FORMULA   2-HAL,4-(NC-N(-R&#39;&#39;)-),6-((-)N(-R)-)-S-TRIAZINE   WHEREIN R AND R&#39;&#39; REPRESENT HYDROGEN OR LOWER ALKYL, BOUND VIA THE -NR-GROUPING TO A RING CARBON ATOM OF THE AFORESAID DYESTUFF.

United States Patent 3,758,470 TRIAZINYL-ANTHRAQUINONES Hans Ackermann,Bottmingen, Herbert Seiler, Riehen,

and Paul Dussy, Basel, Switzerland, assignors to Ciba- Geigy AG, Basel,Switzerland No Drawing. Filed Oct. 16, 197i), Ser. No. 81,598 Claimspriority, application Switzerland, Oct. 17, 1969, 15,581/ 69 Int. Cl.007d 55/20 US. Cl. 260249 2 Claims ABSTRACT OF THE DISCLOSURE New fibrereactive azo, anthraquinone, formazane and phthalocyanine dyestuffs aredescribed which possess as fibre reactive moiety a cyanamide-triazinylgrouping of the formula N Half TN R- wherein R and R represent hydrogenor lower alkyl, bound via the NR-grouping to a ring carbon atom of theaforesaid dyestuif.

These dyes are suitable for the dyeing or printing of organic material,especially textile material made from natural and regenerated celluloseor that made from natural or synthetic polyamides as well as mixedfabric made from cellulose/polyester or polyamide/polyester. The dyeingshave pure and deeply coloured shades, good fastness to Wet processingand are distinguished by a highresistance to acid agents.

The present invention relates to new, valuable reactive dyestufls, toprocesses for their production, to their use for the dyeing or printingof organic material, especially textile material made from natural andregenerated cellulose or from natural and synthetic polyamides, as wellas, as an industrial product, to the organic material dyed or printedusing these new reactive dyestufis.

New reactive dyestuifs have been found corresponding to Formula I:

R N Half Tl I D N EZLCN n D represents the radical of an organicdyestulf,

R and R represent, independently of each other, hydrogen or lower alkyl,each preferably, however, representing hydrogen,

Hal represents fluorine, chlorine or bromine, and

n represents the number 1 or 2.

wherein 'ice metal-containing azo dyestuif, a formazan dyestuff, ananthraquinone or a phthalocyanine dyestuff.

If D is the radical of an azo dyestufi, then it is, e.g. the radical ofa metal-free or metal-containing monoor disazo dyestuif in which a metalatom can be coordinately linked either to one dyestutf molecule or totwo dyestuif molecules. In the latter case, the dyestuffs are known as1:2-metal complex dyestuffs.

The monoazo dyestufis are, e.g. of the class: benzeneazo-benzene,benzene-azo-naphthalene, benzene-azo-pyrazole, benzeneazo-acetoacetylarylide, naphthalene-azonaphthalene andnaphthalene-azo-pyrazole, whilst the disazo dyestufis are of the class:benzene-azo-benzene-azobenzene, benzene-azo-naphthalene-azo-benzene,naphthalene-azo-benzene-azo-benzene and benzene-azo-benzeneazo-pyrazole.

If D is the radical of an anthraquinone dyestufi, then those concernedare preferably 1-amino-4-phenylamino-, -4 diphenylamino or-4-dibenzenedisulphimido-anthraquinone radicals.

If D represents the radical of a phthalocyanine dyestuff, then it ispreferably the radical of an, in particular, sulphonatedphthalocyaninesulphonic acid alkylamide or -arylamide.

If D denotes the radical of a formazan dyestuff, then the dyestuffsconcerned are, e.g. dior tricyclic metal-containing formazan dyestuffs,or also formazanazo dyestuffs.

The mentioned dyestuffs of Formula I may contain, in addition to thecharacteristic Ham FNR N N in the dyestuif radical D, the substituentsusual in dyestuffs, especially in reactive dyestuffs. Such substituentsare, in the first place: halogen atoms such as fluorine, chlorine andbromine; lower alkyl groups such as the methyl, ethyl or propyl groups;ether groups such as the methoxy, ethoxy, benzyloxy or phenoxy groups;N-monoor N,N-disubstituted amino groups; acylamino groups such as theacetylamino and benzoylamino groups; the nitro and hydroxyl groups, aswell as, in particular, watersolubilising groups such as disulphirnidegroups and, in particular, the sulphonic acid group and carboxyl group.

The organic dyestuffs of the initially stated Formula I contain thegrouping either on the dyestuif structure direct, or on externalsubstituents, in the latter case perhaps on the benzene ring ofbenzoylamino or phenylarnino grups, or on w-carbon atoms of loweralkylamino or alkylaminosulphonyl substituents, or also in externalcyclohexylamino groups.

These new reactive dyestuffs are in the form of coloured powders, thecolur of which extends, as a function of the chromophoric system and theauxochromes present, through the whole spectrum, and which, in the formof their alkali salts, are readily soluble in water, in some casesalready at ca. 20 C.

These dyestuffs are suitable for the dyeing or printing of organicmaterial, especially textile material made from natural and regeneratedcellulose such as staple fibre, jute, ramie, hemp and, in particular,cotton, or that made from synthetic polyamides such as nylon, Perlon orBanlon, or natural polyamides such as silk, or especially wool, and alsochlorinated wool, as well as mixed fabric made from cellulose polyesteror polyamide polyester material, whereby the polyester part remainsreserved by these dyestuffs and, optionally, may be dyed or printed witha dis persion dyestuif either simultaneously or separately.

These materials are dyed or printed with the reactive dyestuffsaccording to the invention by methods usual for these substrates.Suitable textile materials are, e.g. fibres, threads, yarns or knittedgoods.

The cellulose material is impregnated or printed at low temperature,e.g. at 120-50 C., with the optionally thickened dyestutf solution, andthe dyestutf then fixed by treatment with acid-binding agents. Suitableacid-binding agents are, e.g. sodium carbonate, potassium carbonate,diand trisodium phosphate, sodium hydroxide, and, at temperatures above50 C., also potassium or sodium bicarbonates. Instead of subjecting theimpregnated materials to an alkaline after-treatment, it is also possible in many cases to add the acid-binding agent, preferably in the formof alkali carbonates, directly to the im pregnating liquors or printingpastes, and then to elfect the development of the dyeing by a shortheating or steaming to temperatures of ca. 100 C. to 160 C., oradvantageously by prolonged standing at room temperature. The additionof hydrotropic agents to the impregnating liquors and printing pastes isadvantageous in this process, e.g. the addition of urea in amounts of to200 g. per litre of dyestutf.

Furthermore, the cellulose material may be dyed with the reactivedyestuifs according to the invention also by the exhaust process,whereby the cellulose material to be dyed is introduced into the dyebath containing an acidbinding agent and, optionally, also neutral saltssuch as, e.g. sodium chloride or sodium sulphate, the bath containing along liquor, i.e. with a ratio of goods to liquor of about 1:10 to 1:50,at slightly elevated temperature; the dye bath is then heated totemperatures of 40, 60 or up to 100 C., and the dyeing process iscompleted at this temperature. The neutral salts accelerating absorptionof the dyestuffs may be added to the bath, optionally, also afterattainment of the actual dyeing temperature.

By the treatment with acid-binding agents, the new reactive dyestuffsare bound covalently to the fibres. The thus obtained cellulose dyeingsare then advantageously soaped to remove non-fixed dyestuif.

Non-fixed dyestuif can be very easily washed out completely, whichconstitutes one of the most essential requirements for good fastness towet processing in the case of the cellulose dyeings produced withreactive dyestuffs.

Natural and synthetic polyamide fibres are dyed in a hot bath, and inmany cases from a neutral to weakly acid bath, e.g. from an acetic acidbath. It is frequently advisable to add compounds containing basicnitrogen, such as fatty acid alkanolamine ethylene oxide condensationproducts, or polyquaternary ammonium compounds, as well as salts such assodium chloride or sodium sulphate. The polyamide dyeings areadvantageously given an aftertreatment with mineral-acid-binding agentssuch as ammonia, disodium phosphate, sodium bicarbonate, orhexamethylenetetramine.

The printing paste required for the printing of cellulose materials isobtained, e.g. by stirring together, at room temperature, urea, anoxidising agent, e.g. the sodium salt of m-nitrobenzenesulphonic acid, athickening agent such as sodium alignate, and an alkali such as sodiumbicarbonate, with Water, to form a stock thickening; and then stirringthe reactive dyestuif into this thickening.

The reactive dyestuffs thus applied by the printing paste are fixed,preferably continuously, in the usual manner, e.g. by a dry heattreatment at 100-180" C., by steaming, especially with saturated steamat 100-105 C. at atmospheric pressure, or with superheated steam atabove C. at atmospheric pressure or at a slight excess pressure,preferably at 102140 C.

To complete the printings, it suffices, as a rule, to rinse cold andhot, to soap them for a short time at boiling temperature, to time againand then dry.

The thus obtained cellulose and polyamide dyeings or printings are pureand deeply coloured, they have a good fastness to wet processing, andare distinguished, in par- D represents the radical of an organicdyestufi', R represents hydrogen or a lower alkyl group, and nrepresents the number 1 or 2,

with n moles of a triazine compound of Formula III:

N HaIT wNH-GN l N \i/ Hal wherein (III) wherein Hal represents fluorine,chlorine or bromine, to give a reactive dyestuffs of Formula Ia:

N i Half fi-ND NHCN 11 wherein D, R, n and Hal have the meanings givenunder Formulae II and III; or in building up the dyestuff of Formula Iafrom components of dyestuffs D, of which components at least onecontains the radical of Formula Hal (Illa) bound by way of the aminogroup NR-; and, optionally, alkylating in the final dyestuflt of FormulaIa the nitrogen of the cyanamide group with an alkylating agent.

The dyestutfs of Formula II containing amino groups, usable as startingdyestuffs, preferably those wherein R represents hydrogen, are, e.g.aminoanthraquinones such as, e.g. 1-amino-4 (morp-aminophenylamino)-anthra quinones and their sulphonic acids;aminophthalocyanines such as condensation products ofphthalocyaninesulphonic acid chloride with alkylenediamines or withoptionally sulphonated phenylenediamines, as well as aminoformazandyestuffs and aminoazo dyestuifs. The last-named contain amino groups tobe acylated, in the coupling component and/or in the diazo component.

The starting dyestuffs of Formula II containing NHR- groups are obtainedusing production processes known to the expert.

The compounds usable according to the invention, of

which are new and which introduce into the end dyestuffs of Formula Ithe radical of Formula 11121, are obtained, e.g. by the reaction of2,4,6-trichlorotriazine, 2,4,6-tribromotriazine, or also2,4,6-trifluorotriazine, with at least 1 mole of cyanamide; it isadvantageous thereby to use the alkali salt, especially the sodium salt,in aqueous solution at a temperature of ca. -10. The preferred 2,4-dichlorotriazine-G-cyanamide is thereby obtained as colourless solidsodium salt, which can be isolated by salting out.

The reaction of the amino dyestuffs of Formula II with compounds ofFormula III is performed in the usual manner, advantageously in aqueousmedium, optionally in the presence of inert, easily removable organicsolvents such as lower aliphatic ketones, e.g. acetone, and preferablyin the presence of mineral-acid-butfering agents such as sodium orpotassium carbonate, sodium or potassium hydroxide, dior trisodium ordior tripotassium phosphate, or sodium or potassium acetate, attemperatures of about 40 to 60 C.

After completion of the reaction, the finished reactive dyestuif ofFormula Ia is salted out from its preferably pre-neutralised solution orsuspension using sodium chloride or potassium chloride, filtered offunder suction, washed and dried. The new dyestuffs are advantageouslydried with a moderate heat and, optionally, under reduced pressure.

On the other hand, the dyestufis of Formula Ia are also obtained bybuildup from components D, which components contain at least one radicalof Formula Illa bound by way of the amino group -NR. This procedure isespecially suitable for the production of azo dyestuffs by coupling ofan aromatic diazonium compound with a coupling component, of which atleast one contains the characteristic group according to the inventionof Formula IIIa.

For example, a diazonium compound of an amine of Formula IV:

wherein A represents an optionally further substituted radical of anaromatic diazo component, and R and Hal have the meanings given underFormula I,

is coupled with a coupling component B-H to give an azo dyestuif ofFormula V:

Hal

If in the radicals A and B there are in o-position to the azo groupmetallisable substituents such as, e.g. a hydroxy or carboxyl group,then, optionally, the thus obtained metallisable azo dyestuffs can befurther reacted with metal-introducing agents to metal-containing azodyestuffs.

Another variation of this process consists in coupling a diazoniumcompound of an amine of the Formula A-NH with a coupling component ofFormula VI:

wherein R and Hal have the meanings given under Formula Ia,

and

B represents the radical of a coupling component, to give a dyestulf ofFormula VII:

Hal (VII) and, optionally, converting the obtained dyestutf, providedthat it contains in A and B in o-position to the azo bridge metallisablesubstituents such as the hydroxyl group or the carboxyl group, withmetal-releasing agents into the corresponding metal complex dyestufi.

Applicable as the diazonium compound for this purpose are diazotisedaromatic amines common in azo dyestuifs, e.g. optionally sulphonatedphenylor naphthyldiazonium compounds.

Coupling components are, e.g. aminonaphtholsulphonic acids oraminoacrylpyrazolones or -pyrazolimines, as well asacetoacetylaminoarylides.

Azo dyestuffs having two triazinyl groups of Formula IIIa are, amongstother ways, also obtained by coupling of a diazonium compound of FormulaIV with a coupling component of Formula VI.

The coupling is performed, in the usual manner, in weakly acid to weaklyalkaline medium.

Both the coupling and, optionally, also metallisation withmetal-releasing agents such as copper salts, chromium salts, nickelsalts or cobalt salts, must be carried out under carefully regulatedconditions, i.e. with the avoidance of high pH-values and temperatures.

Metal complex dyestuffs thus obtained can then be reacted with one moleof a further metallisable azo dyestulf to give 2: l-complex dyestufis.

A modified embodiment for the production of these reactive dyestufis ofFormula I consists in condensing a dyestufi containing triazinyl groups,of Formula VIII:

n- NR-J al 11 (VIII wherein D, R, Hal and n denote that stated inFormula Ia, with at least n moles of cyanamide or, advantageously, ofits alkali salt such as sodium salt, to give a reactive dyestuif ofFormula Ia; and, optionally, alkylating the nitrogen of the cyanamidegroup with an alkylating agent.

The starting materials of Formula VIII are obtained, e.g. by reacting,in the usual manner, a dyestuff of Formula 11 containing amino groupswith 2,4,-6-tri-chloro-, -bromo-, or -fiuoro-1,3,5-triazine.

The reaction of the dyestu'ff of Formula VIII containing triazinylgroups with cyanamide or with its alkali salt, preferably the sodiumsalt, is performed at a temperature of 40-'60 C. in aqueous medium.

After completion of the reaction, the finished reactive dyestuff ofFormula Ia is salted out, filtered off under suction, washed and dried,as described in the first process.

In the thus obtained dyestufis of Formula la, the nitrogen of thecyanamide group can, if so desired, be alkylated by reacting thedyestufis of Formula Ia with, advantageously, an excess of alkylatingagents such as, e.g. dimethyl sulphate or diethyl sulphate attemperatures of 40-55 C. in aqueous medium.

In this way, the reactive dyestuffs of Formula I, wherein R representslower alkyl are obtained.

The following non-limitative examples serve to illustrate the invention.The temperatures are given in degrees centigrade, and the ratio of partsby weight to parts by volume is as g. to cm.

2 I OaH SOsHfiOS 03H An amount of g. of 2,4-dichloro-6-cyanamide-1,3,5-triazine is added to a solution of 50.3 g. of the monoazo dyestuifproduced from diazotised 1,3-diaminobenzene-4- sulphonic acid coupled to1-hydroxy-naphthalene-3,6-disulphonic acid, in 1000 ml. of water atabout -55". The pH-value is maintained at ca. 7.0 to 7.5 by the additionof soda solution, and stirring proceeds for ca. 5 hours at a temperatureof 45-50. As soon as the condensation reaction is finished, the formedreactive dyestufI of the above formula is precipitated with potassiumchloride, filtered ofi, washed with dilute potassium chloride solution,and dried in vacuo at -85.

The reactive dyestutf is in the form of a red powder which dissolves inwater to give an orange-red colour.

The 2,4-dichloro-6-cyanamide-1,3,5-triazine used as starting product isobtained by suspending 37 g. of cyanuric chloride in a mixture of 200 g.of ice and 20 g. of acetone, whilst vigorous stirring is maintained; andthen adding dropwise at 0', so that the pH-value is held between 9.0 and10.0, a solution of 17.2 g. of disodium cyanamide in ml. of water. Afterthe dropwise addition, stirring is continued for about 12 hours at 05and the formed suspension is dissolved by the addition of water. By theaddition of sodium chloride, 2,4-dichloro- 6-cyanamide-1,3,5-triazine isprecipitated; it is then filtered 01? and washed.

Reactive dyestutfs having similar properties are obtained by condensingthe dyestuffs containing amino groups listed in column II of thefollowing Table 1 with the triazine compounds given in column III, asdescribed in Example 1. The shades of the dyeings on cotton with theobtained reactive dyestuifs are shown in column IV of the same table.

TABLE 1 1 n 111 IV Ex. Shade on No Dyestufl 'Inazlne compound cotton 2 NY HgN- SOsH (ll-Jr ]NHCN e w N: CH3 \/N Same as above..:.-.::: Greenishellow;

mN- SOaH y Yellow.

no \N/ SOaH TABLE 1Continued I II III IV Ex. Shade on No. DyestuffTriazine compound cotton 23 S 0 H 011 N Orange. 011 NHON N N\/ N SOaHNH: I I 01 S 0 11 24 lS031 11 .do Reddish orange.

SOaH NH-CH:

25 --do Bluish red.

S 03H OH NH-C O I N: NE:

S 0 2H- S O :H S 0 11 26 SOs .--d0 Orange.

N=N N=N NH;

27 do Yellow.

HzN =N S 03H l CH N--N '-I OH;

N HO N 28.-.- S Oa -do Orange.

N=N- N=N l S 0311 CH I NH:

29.... S 3 -dO D0.

N=N N=N NH:

I Q I S 03H 30 2 11TH: H S 0311 do Blue-black.

I S 0 H S 0311 NH:

31 C11 do Ruby.

/ O I O E I HOaS- N=1 I S 0311-- NHQ TABLE 1-Continued I II III IV Ex.Shade on No. Dyhstufl Trizaine compound cotton 40 Cu N Ruby.

$03K OCH}; SOaH- 30 K 42 OHN N Black brown.

I Br-f j-NHCN H03 S S 03H N N M V OzN S 03H NH:

44...:r: NO: Same as a'b0ve..':;::: Do.-

SOQH SOaH u NH:

0 E o NH: I i I 45...::: S 0 H Greenish yellow.

TABLE 1Continued I II III IV Ex. Shade on No. Dyestufl Triazine compoundcotton 45a..- N Red.

11m $0311 c1I W-NHCN T N N HO S \[SOaH 45b- NH: :----do Yellow HOaS \N/HO S SOQH

EXAMPLE 46 filtered off, washed with dilute sodium chloride solution,

C1 and dried in vacuo. N l The dyestufi? is in the form of a red powderwhich 8033 OH dissolves in water to give an orange-red colour.

I N NH CN EXAMPLE 48 SOQH SOaH N 01 SOZH SlOsH OH IfH- N N A solution of20.3 g. of cyanuric chloride in 120 ml. of N=N acetone is added dropwiseto 100 ml. of water at 0. To the obtained finely dispersed dispersion isadded dropwise S0311 S0311 within 1 hour a solution of 63.3 g. of thedyestufi 0btained from diazotised 2-naphthylamine-1,5-disulphonic SIOEHacid coupled with 1-amino-8-hydroxynaphthalene-3,6-disulphonic acid, in700 ml. of water at 0; the pH-value is maintained between 6 and 7 by theaddition of soda soluamount of of the lyestufi: Obtamed accord tion, andthe solution is stirred for ca. 12 hours at 05. 5 mg to Example 1Sdlssolved 111 1100 P W to The dyestufi Solution is Subsequently heatedto 40450, the obtainedsolution are added at 40-50", within 1 hour, andto it is added dropwise at this temperature, within 30 9 of dlethylSulphate, the PHVaIue be1-T1g flf minutes, a solution of 9.5 g. ofdisodium cyanamide in mamtamed w 6 and 7 by the drPpwlse addltlQn of m1.of water. The dyestufi is afterwards salted out with an aqueoustrlsodlllm phosphate solution. The ethyla ted sodium chloride, filteredoff, washed with dilute sodium 50 dyestuff of the above formula 15Preclplfated by addltlon chloride Solution and then dried in vacuo ofsodium chloride, filtered oft", washed with diluted sodium The dyestuffof the above formula is in the form of a chlonde Solutlong n dnedvacuored powder which dissolves in water to give a bluish red dy'eswfi1s m P of a red Powder Whlch colour. dissolves in water to give a bluishred colour.

EXAMPLE 47 CH1 EXAMPLE 49 C1 N-CN N T c1 NHCN N N I \I/ N N sour 0H NHSOaH S 0311 SOaH SO3HAK/ SOaH An amount of 15.7 g. of the dyestufi'produced accord- An amount of 31.9 g. of l-amino-S-hydroxynaphthaling toExample 1 is dissolved in 1000 ml. of Water; to the ene-3,6-disulphonicacid is dissolved at 35-40 in 200 parts solution are then added dropwiseat 4050, within 1 of water with sodium hydroxide solution, with apH-value hour, 100 g. of dimethyl sulphate, the pH-value being of 6.5.The solution is then adjusted to a pH-value of 4; thereby maintainedbetween 6 and 7 by the addition of to the solution are added 20 g. of2,4-dichloro-6-cyanasoda solution. The methylated dyestuff of the aboveformido-1,3,5-triazine, and the pH-value of the reaction mixmula isprecipitated by the addition of sodium chloride, ture is therebymaintained at 3 by the addition of sodium carbonate solution. Aftercompleted condensation, 30 g. of sodium bicarbonate are added to thesolution, and a solution of 18.7 g. of diazotised1-amino-4-methylbenzene- Z-sulphonic acid is then added. As soon as thecoupling is 22 A solution of 20.3 g. of cyanuric chloride in 100 ml. ofacetone is added dropwise at into 100 ml. of water. To the thus obtainedfinely dispersed dispersion is added dropwise within 1 hour, withstirring, a solution of 48.9

finished, sodium chloride is added to the reaction mixture, 5 g. of1-amino-4-(3'-amino-4'-sulphophenylamino)-anthrathe precipitateddyestuff filtered off, and washed with soquinone-Z-sulphonic acid in 300ml. of water at 0; and dium chloride solution. After drying in vacuo, ared powthe pH-value is held between 6 and 7 by the addition of der isobtained which readily dissolves in water to give soda solution.Stirring then proceeds at 0-5 for ca. 12 a red colour. hours. Thedyestutr suspension is subsequently heated to If cotton or staple fibreis dyed or printed with this 40-50, to it is then added dropwise within2 hours a dyestutf by the usual processes for reactive dyestufis, thensolution of 9.5 g. of disodium cyanamide in 50 m1. of Nd dyeings orPrintings are Obtained v g very g water; the anthraquinone dyestuff ofthe above formula fastness properties. is subsequently salted out withpotassium chloride, fil- EMMPLE 50 tered 0E, washed with potassiumchloride solution, and

15 dried in vacuo. NE: The dyestuff is in the form of a blue powderwhich dissolves in water to give a blue colour.

S0311 If, instead of the 48.9 g. of 1-amino-4-(3'-amino-4'-sulphophenylamino)-anthraquinone 2 sulphonic acid V mentioned in thisexample, equivalent amounts of the II anthraquinone compounds listed inColumn II of the 0 SOaH following Table 2 are used, with the procedurebeing otherwise as stated in Example 50, then dyestuifs are obtainedhaving similar properties. The shades of the N cellulose dyeingsproduced with the final products are NEON given in column III of thesame table.

TABLE 2 I II III Example Shade on number Anthraquinone compoundcellulose 51...-.--.-.- t I qH; Blue.

Hots Osmn Y SOsH 52 ..:T.:.: h) NH: D0.

/\ son:

4) 111E -CH$ SOr-NH-SOFQ NH:

53...:-.::;: O NH; Greenish I blue.-

e HO CH:

i) NH CH:

sm-nn-soQ NH;

54...:::..: f) IIIH: Blue:

/\ son:

( NH 802K TABLE 2-Continued I II III Example Shade on numberAnthraquinone compound cellulose 55 (I) IIIHQ B1116.

HOaS 08 OaH Y NH S 03H 56.1...222: (I) llqHg DO.

Hog S 57...'..:::-:: NH: D0.

A s 01H NH- S 0311 58...:125: IITH: DO

0 NHQ s 0311 59 O NH: Gl'eeuish l blue.

61 O NH: D02

NH: D0.

TABLE 2Con1'inued I II III Example Shade on number Anthraquinonecompound cellulose 63 O NH: Greenish A blue. 0 s om HO S S 0 11 u I I oNHQNH:

64. IOl NH: D0.

Hogs- O NH- NH:

I S 03H 65 O NH: Blue.

I NH:

66- 0 NH: Greenlsh A I blue. H0 30 s 0 H l Q NH:

A s 03H 68 0 lf a Blue:

S OaH O NH- S 0 H 69 0 N z Greenish blue.

TABLE 2Contlnued I II III Example Shade on number Anthraquinone compoundcellulose 70 NH: Greenlsh blue.

Y sour Alter-sulphonated:

71 H038 0 N Blue:

l E035 NH NH:

72 0 NH; D0;

NH-Q-ChQH-Q-Nm 73 0 NH: Reddlsh l blue.

V CB; SOT-NH:

l CH1 74.: ...m. 0 NH: Greenlsh l blue.

b NH-Q-OHr-NH:

75 (I) IIIH: Blue.

A s 03H Y CH3 0 NHCHr-NH S OsH EXAMPLE 76 group is saponified. Thedyestuff is then isolated by fil- An amount of 57.6 g. of copperphthalocyaninetetrasulphonic acid chloride is suspended in 500 ml. ofwater and 300 g. of ice; the suspension is then stirred with 15 g. ofm-aminoacetanilide, and adjusted to a pH-value of 7 by the addition ofaqueous ammonia solution. The

heated for 3 hours to 8590, whereby the acetylamino tration; it is againsuspended in 1000 parts of Water at 0-5", and the pI-I-value of thesuspension adjusted with dilute sodium hydroxide solution to 8.0. Tothis suspension are added 21 g. of cyanuric chloride. Condensation isperformed at 05, whilst the suspension is well stirred, and thehydrochloric acid being liberated is neutralised by dilute sodiumcarbonate solution being added dropwise. As soon as condensation isfinished, the temperature is raised to 4055, and a solution of 9.5 g. ofdisodium cyanamide in 50 ml. of water is added dropwise within 2 hours.After completed reaction, the new dyestulf of the following constitutionis salted out, filtered 29 off, and dried at 50-60 in vacuo. Itcorresponds to the following formula:

-802 NH CuPe I (so X) Cl \N )NHCN wherein Pc represents thephthalocyanine structure, and X represents in some cases NH and in somecases -ONa or ONH The dyestuif dyes cellulose or polyamide fibres inpure turquoise blue shades having fastness to Wet processing. If,instead of the condensation product from 57.6 g. of copperphthalocyaninetetrasulphonic acid chloride and 15 g. ofm-aminoacetanilide (saponified), the copper phthalocyanine dyestuffslisted in the following Table 3, column II, are used, the procedurebeing otherwise analogous to that described in Example 76, then reactivedyestuffs are obtained having similarly valuable properties, whereby theshade of the cellulose dyeing produced therewith is given in column IIIof the same table.

TABLE 3 Turquoise blue.

Formazan compound or formazanazo compound 30 EXAMPLE 79 HOaS- An amountof 86.1 g. of the aminoformazanazo dyestuff of the following formula isdissolved in 1000 ml. of water; to this solution are then added 20 g. of2,4-dichloro-6-cyanamido-1,3,5-triazine, and the whole is stirred at 50until condensation is completed. During the reaction, the pH-value ismaintained at 67 by the dropwise addition of sodium carbonate solution.As soon as no further starting dyestutI is detectable, the reactivedyestutf of the above formula is precipitated by the addition ofpotassium chloride, filtered 01f under suction, washed with potassiumchloride solution, and dried in vacuo.

The dyestufi is in the form of an olive-coloured powder which dissolvesin water to give an olive colour.

If, instead of the 86.1 g. of the aminoformazanazo dyestuff, equivalentamounts are used of the formazan dyestuffs or formazanazo dyestuffsgiven in Table 4, column II, the procedure being otherwise as describedin Example 79, then reactive formazan or formazanazo dyestuffs havingsimilarly valuable properties are obtained. The shades of the dyeings oncotton are listed in column III of the same table.

TABLE 4 II III Shade on cellulose fibres N H: Blue.

.31 32 TABLE 4Continued I II III Shade on Example cellulose NumberFormazan compound or formazanao compound fibres 81 NH: Blue.

S 03H r l? N /N 82 S 03H D0.

0 o o 0 HOBS- S 0311 N N H l N\ /N C 1 82a NH: S 0311 D0;

/0 n S 0311 N N HOaS l, 1

EXAMPLE 83 the bath contains 50 g. thereof per litre. In the course of aCotton or staple fibre is impregnated at -25 with a solution containing20 g. of the dyestulf described in Example 1, 50 g. of sodium sulphateand 20g. of calcined sodium carbonate; it is then squeezed out to give aweight increase of 80 to 100% rolled up, and stored for 4-24- hours atroom temperature. After rinsing and soaping, a pure red deying isobtained which possesses an outstanding fastness to washing, and a verygood fastness to light.

EXAMPLE 84 Cotton is padded at 20 with a solution containing 2% of thedyestuif described in Example 1, and then dried. After drying, thematerial is padded with a solution containing 1% of sodium hydroxide andof sodium chloride; it is then steamed for 30 seconds at 100-103 Afterrinsing, and soaping with boiling, a very pure red dyeing is obtainedhaving fastness to boiling.

EXAMPLE 85 Cotton is introduced at 20-25 into a dye bath (ratio of goodsto liquor=1 containing, relative to the cotton, 2% of the dyestuffdescribed in Example 1. Within 30 minutes, sodium sulphate is added inportions until further hour, 10 g./ litre of calcined soda are added,and the temperature simultaneously raised to 35. After completed dyeing,the material is rinsed, and soaped whilst being boiled. An even reddyeing is obtained having very good fastness to wet processing.

EXAMPLE 86 An amount of g. of polyamide fibres is heated to boiling forone hour in a dye bath containing in 3000 ml. of water 2-g. of thedyestuif obtained according to Example and 2 ml. of formic acid. Afterthe material has been rinsed, a bluish red dyeing is obtained having anexcellent fastness to wet processing and to light.

EXAMPLE 87 An amount of 2 g. of the dyestuff obtained according toExample 1 is dissolved in 5000 ml. of water at 40; to this solution arethen added 0.5 g. of a condensation prodnot of ethylene oxide withstearylamine and 6 ml. of 30% acetic acid. 100 g. of wool are introducedinto the thus obtained dye bath, the bath is heated within 30 minutes toboiling, and the material dyed for one hour at this temperature. Afterrinsing a bluish red dyeing is ob- 3 3 tained having good fastness tolight, rubbing and to washing.

EXAMPLE 88 A cotton fabric is padded at 20-25 with a solution containingper litre of water 20 g. of the reactive dyestuff according to Example1; the material is squeezed out to a liquid absorption of 80%, and driedfor 1 minute at 100. The thus pre-treated material is then padded with asolution containing per litre of water 250 g. of sodium chloride and 15g. of 30% aqueous sodium hydroxide solution; it is squeezed out to givea liquid absorption of 80%, and afterwards exposed to the air for 10-30seconds at 2025. The material is thereupon soaped for 10 minutes in abath at 9598 containing 2 g. of soap per litre; and is subsequentlyrinsed and dried. A red cotton dyeing is obtained.

EXAMPLE 89 A printing plaste is roduced by stirring together 330 m1. ofWater, 200 g. of urea, 10 g. of sodium salt of m-nitrobenzenesulphonicacid, 395 g. of 5% sodium alginate thickening and 25 g. of sodiumbicarbonate, at room temperature (20 C.), to form a stock thickening; anamount of 40 g. of the reactive dyestulf according to Example 1 is thenstirred into this thickening.

If a cotton fabric is printed with this printing paste, and the driedfabric steamed for 60 seconds at 101-103, soaped, rinsed and dried, thena red printing is obtained.

34 We claim: 1. A reactive dyestuff of the formula sogn (HO3S)m l IR'CNin which Z is a divalent bridging member of the benzene or cyclohexaneseries, R and R are, independently of each other, hydrogen or low alkyl,Hal is fluorine, chlorine or bromine, and m is 0, 1 or 2.

2. A reactive dyestufi according to claim 1, wherein R and R eachrepresents hydrogen and Hal represents chlorine.

References Cited UNITED STATES PATENTS 3,399,194 8/1968 Mangini et a1.260-249 JOHN M. FORD, Primary Examiner US. Cl. X.R.

